Method of making motor fuel



. amphoteric oxides.

Patented Nov. 21, 1944 UNITED STATES;

METHOD OFMAKING MOTORYFUEL i Joseph m y James, Pittsburgh,'Pa assignorto Clarencel. Byrn'es, Pittsburgh; Pa.-, as--trus-- No DrawingApplication September 14, 194%.

,. SerialNo. 356,833

9 Claims... (01. 136 511); l

-In..,a.-.number of patentssuch as United States- Patent Nos.1,697,653..of.Jan. 1, 1929 (Reissue 18,522), 1,859,587, 1,948,817,2,01'0,085,.2,010,086,

2,036,215, 2,054,571; 2,085,221, and. 2,085,499, I 1

have described processes for makingpartial oxidationproducts fromaliphatic and naphthenic hydrocarbons, such as petroleum fractions,shale. oil, and oils from the low temperature distillation: of,.coal.In. such process, the vaporized. or finely dividedhyclrolcarbonis mixedwith oxygen or an oxygen containinggas andpassed througha re-. actionzone, preferably in contact witha catalyst, at atemperature below thatof continuous self-:- sustained complete, combustion, and preferablybelow a red heat.

Th product when condensed. or absorbed and; recovered containspartialoxidationproducts in; a range from alcohols to oxygenated organicacids, including aldehydes, ketones, esters, ethers, lac. tones, etc.Many or all of these bodies are pres: ent in different molecularWeights.

.In thisstep of oxidation I prefer to proportion thevariable factors sothat a large percentage of I alcohols is formed as disclosed in my US.Patents 1,7 9 0 @Qlfiiilii'l w th're t ely s a id; though this is notessential, In the oxidation step someacids are formedand there are someincisuch as chlorides, nitrates, and sulfates;- while with strongbases-they form; salts inwhich the aluminum functions as an acid formingwith sodium and potassium their aluminates. I have also? found-that zincchloride (especially when anhydrous) also" functions similarly as adehyv and the fraction Within the gasoline or motor fuel;

'- range is separatedfrom other andheavier frac-,

dental reactions such as cracking, forming of un- I saturatedhydrocarbonsor derivatives, aromatics,

ring body hydrocarbons to, some extent, ,de,-,

pending upon the ratios of the Variable factors inthe partial oxidationstepr I The. present, invention is based uponmy dis coye ies relative toformation of aromatics and I nap henes which I can obtain duringcracking onlthelrmal v decomposition of V the product mixture [resultingfrom the oxidation step. These dis-.

, ies are that if certain dehydrating catalysts areemployedin thecrackingstep; they act to eliminate the elements of Water (0H1 and H),

from remote pointsin the hydrocarbon chains,;

resulting, in the formation of material or large.

percentages. of ring compounds such as aromatics or,,naphthenes.in. theproduct. This changeis especially desirable in making motor fuels andis. enhanced by properly" adjustingthe thermal conditions .of-;catalytic cracking with catalysts of such a grouplor class. Thepreferable type-of oxide catalysts in such a class is that of inorganic'In this type I have. found. thataluminumoxides are of high value,though oxidesof. zinc. or tin (or of some rare elements suchasigallium).may be used. Such amphotericl oxideshave thepropertiesof both acidic andbasic oxides, since ;.with strong: acid they formisalts tions. Thiscontainshydrocarbons, some oxygen. corn-pounds, unsaturateds, andaromatic, and, naphthenic bodies. In carryin out my improved process formaking motor fuels. of good or high octane rating, I preferablyneutralize or saponify and absorb any acids present in the oxidationproduct, before cracking. However, thisis not essential and'may beomitted especially where vpartial oxidation of petroleum fractions inthe vapor phase is. used and where the vapor exit stream from theoxidation chamber'ispassed on through the cracking unit or units.Catalytic cracking as herein disclosed may be carried out either in theliquid phase where the vapors from oxidation ,are con densed, or in thevapor phase orboth. In each case sufficient ring orv cyclic compoundsofthe naphthenic or aromatic types may be formed to impart materialanti-detonating characteristics to the resulting motor fuels.

I will now: give some specific examples:

Example 1.--A portion of ordinary commercial cracked gasoline, oxidizedby my Well known' vapor phase catalytic method ,disclosed in my UnitedStates patents before recited herein and containing different oxygenderivatives in. the

' range from alcohols through aldehydes to and including organic acidswith similar derivatives of different molecular weights, was subjectedto my vapor phase catalytic cracking step as follows:-

A smooth steel. tube 2 inches in diameterby 14.: inches long was mountedin a hot airbathwith:

i a thermocouplezin. a .we'll'in the tubeicentel. fort:

giving the vapor temperature. The tub was filled with catalyst ballsabout the size of grapes or about 1 centimeter in diameter made of 90%by weight of Bakers C. P. aluminum oxide ce- .mented by about by weightof bentonite Per cent by volume Olefines and oxidized bodies 31.4Aromatic hydrocarbons 49 Naphthenic hydrocarbons 19.6 Saturatedaliphatic hydrocarbons 0 Example 2.--A run similar to (1) above, wasmade with anhydrous zinc chloride as the catalyst and a temperature of325 C. The yield of liquid product was 91% by volume, and its analysisshowed:

Percent by volume Olefines and oxidized bodies 32.2 Aromatichydrocarbons 24.8 Naphthenic hydrocarbons 23.8 Saturated aliphatichydrocarbons 19.2

This again shows violent changes in this complex mixture with adifferent catalyst and with reactions like the above taking place at arelatively low temperature.

In both cases there was a great increase in the percentage of aromaticand naphthenes, due to the peculiar dehydrating effect of the catalyst,carrying such percentage beyond and preferably beyond and thus givingmaterial anti-detonating characteristics thereto.

The desired reactions to give the result are probably of two kinds: thehydrogen on carbon atom remote from a carbon atom holding a hydroxylgroup reacted with the hydroxyl group; and/or a similar reactionoccurred between two remote hydroxyl groups. These are illustrated inthe following equations:

in either or both cases ring compounds form to a sufficient extent togive the desired anti-knocking and high octane rating. Thenon-condensible vapors and gases from both oxidizing and cracking stepsmay be polymerized into gasoline, the gases from cracking may berecirculated through the cracking still to give nucleating" oralkylation as set forth in other of my copending applications, and manyother changes may be made without departing from my invention. Thecatalytic cracking with my improved catalysts may be carried out in thevapor or liquid phase or both. The oxidation may be carried out in theliquid phase, though I prefer my vapor phase process.

I claim:

1. In the method of making motor fuel, the

steps comprising partially oxidizing a petroleum fraction in thepresence of free oxygen to produce a product containing a mixture ofoxygen derivatives of hydrocarbons of different molecular weights in therange from aliphatic alcohols to oxygenated organic acids, thereafterthermally decomposing at a temperature of at least about 325 C. aportion of the product containing hydrocarbons of greater carbon contentthan gasoline under superatmospheric pressure in the presence of adehydrating catalyst capable of dehydrating the hydrocarbons under saidthermal decomposing conditions to produce a fuel of lower average carboncontent than said product and which contains cyclic bodies to a materialamount, and then fractionating the cracked product to produce motorfuel.

2. In the method of making motor fuel, the steps comprising partiallyoxidizing a petroleum fraction containing a mixture of normally liquidhydrocarbons of different molecular weight from the group of aliphaticand naphthenic hydrocarbons in the presence of free oxygen to produce aproduct containing a mixture of oxygen derivatives of hydrocarbons ofdifferent molecular weights in the range from aliphatic alcohols tooxygenated organic acids, thereafter thermally decomposing at atemperature of at least about 325 C. a portion of the product containinghydrocarbons of greater carbon content than gasoline in the presence ofa dehydrating catalyst capable of dehydrating the hydrocarbons undersaid thermal decomposing conditions to produce a fuel of lower averagecarbon content than said product and which contains cyclic bodies to amaterial amount, and then fractionating the cracked product to produce amotor fuel.

3. In the method of making motor fuel, the steps comprising partiallyoxidizing a petroleum fraction in the vapor phase at an elevatedtemperature in the presence of free oxygen to produce a productcontaining a mixture of oxygen derivatives of hydrocarbons of differentmolecular weights in the range from aliphatic alcohols to oxygenatedorganic acids, thereafter thermally decomposing at a temperature of atleast about 325 C. a portion of the product containing hydrocarbons ofgreater carbon content than gasoline in the presence of a dehydratingcatalyst capable of dehydrating the hydrocarbons under said thermaldecomposin conditions to produce a fuel of lower average carbon contentthan said product and which contains cyclic bodies to a material amount,and then'fractionating the cracked product to produce a motor fuel.

4. In the method of making a motor fuel, the steps comprising partiallyoxidizing a petroleum fraction in the vapor phase 'at an elevatedtemperature inv the presence of free oxygen to produce a productcontaining a mixture of oxygen derivatives of hydrocarbons of differentmolecular weights in the range from aliphatic alcohols to oxygenatedorganic acids, thereafter thermally decomposing at a temperature of atleast about 325 C. a portion of the product containing hydrocarbons ofgreater carbon content than gasoline in the vapor phase in the presenceof a dehydrating catalyst capable of dehydrating the hydrocarbons undersaid thermal decomposing conditions to produce a fuel of lower averagecarbon content than said product and which contains cyclic bodies to amaterial amount, and then fractionating the cracked product to producemotor fuel.

5. In the method of making motor fuel, the steps comprising partiallyoxidizing a petroleum fraction in the presence of free oxygen to producea product containing a mixture of oxygen derivatives of hydrocarbons ofdifferent molecular weights in the range from aliphatic alcohols tooxygenated organic acids, thereafter thermally decomposing at atemperature of at least about 325 C. a portion of the product containinghydrocarbons of greater carbon content than gasoline under higherpressure in the presence of a dehydrating catalyst capable ofdehydrating the hydro-carbons under said thermal decomposing conditionsto produce a fuel of lower average carbon content than said product andwhich contains cyclic bodies to a material amount, and thenfractionating the cracked product to produce motor fuel.

6. In the method of making a motor fuel, the

steps comprising partially oxidizing a petroleum fraction in thepresence of free oxygen to produce a product containing a mixture ofoxygen derivatives of hydrocarbons of different molecular weights in therange from aliphatic alcohols to oxygenated organic acids, andthereafter thermally decomposing the product at a temperature -a productcontaining a mixture of oxygen derivatives of' hydrocarbons of differentmolecular weights in the range from aliphatic alcohols to oxygenatedorganic acids, and thereafter 'thermally decomposing the product at atemperature of at least about 325 C. inthe presence of, a dehydratingcatalyst from the group consisting of aluminum oxide and zinc chloridecapable of dehydrating thehydrocarbons under the said thermaldecomposing conditions.

8. In the method of making motor fuel, the steps comprising partiallyoxidizing apetroleum fraction in the presence of free oxygen to producea product containing a mixture of oxygen derivativesof hydrocarbons ofdifierent molecular weights in the range from aliphatic alcohols tooxygenated organic acids, and thereafter thermally decomposing theproduct at a temperature of at least about 325 C. in the presence of adehydrating catalyst capable of eliminating hydroxyl elements of waterfrom remote points in the hydrocarbon chains to form ring compounds.

9.,In the method of making motor fuel, the steps comprising partiallyoxidizing a petroleum fraction in the presence of free oxygen to producea product containing a mixture of oxygen derivatives of hydrocarbons ofdifferent molecular weights in the range from alcohols to oxygenatedoxidation product and which contains a material proportion of cyclicbodies.

JOSEPH I-IIDY JAMES.

